Substantially nongelling zein coating composition



Patented Dec. 26, 1939 SUBSTANTIALLY NONGELLING ZEIN COATING COMPOSITION Roy E. Coleman, Meriden, Oonn., assignor to The Zein Corporation of America, a corporation of Delaware No Drawing. Application January 28, 1938,

Serial No. 187,559

11 Claims.

In the following description of my invention 1 refer to solutions of zein derived from corn, but it is, of course, to be understood that my inven- 15 tion is also applicable to solutions of the other prolamlns such as, for example, gliadin irom wheat, hordein from barley, kafirin from kaiir and the prolamlns from other cereal grains.-

The above-mentioned prolamlns areat present so ordinarily derived by extraction of thegluten of corn or other cereal grains with an aqueous alcohol solution in which the added water varies generally from about 8 to 40% of the solvent mixture, the extract so produced being dried, forming a dried prolamin extract which may be completely dried, or in commercialform containsa small percentage of moisture. Such prolamin extracts, such as zein extracted from corn, may be used in accordance with my invention, 30 although zein or other prolamins obtained in any other suitable manner may also be used.

In my prior applications referred to above, I have described solutions and liquid coating compositions containing prolamins'and particularly 35 zein which are anhydrous or substantially anhydrous and which, in concentrations in which the proportion of solvent to. zein is from about 2:1 upward,,and more, and particularly from 4 to 5:1, are stable in the cold in that they do not separate 40 or form and deposit a separate phase or layer containing largely zein with a supernatant layer of liquid consisting largely of solvent. The formation of such stable solutions is .important in connection with the utilization of zein and similar prolamins in the production of coating compositions and the like, since they enable the zein to be put in a homogeneous and usable form either for direct use or for compounding with other materials, solvents, non-solvents, coating and thicken or to become'heavier in body; and in many cases to gel. Such tendencies to increase in viscosity, or to gel, while not preventing the.

utilization of the compositions immediately or within short periods after preparation, do impose serious limitations on their wide-spread commercial application and utilization, since the materials must remain stable and reasonably constant in their characteristics during the periods necessary fortransportation and distribution either in bulk or in packages, and to permit of reasonable periods of storage.

In accordance with the present invention, I have developed solutions containing prolamlns and particularly zein and methods of making the same whereby the tendencies to gel, in which I include the tendency to increase in viscosity which is ordinarily a preliminary of gelling, are retarded and in many cases completely prevented, so as to greatly increase the field of applicability, and permit wider distribution and conventional handling of the manufactured products without material change in characteristics or solidification by gelling over such reasonable periods of time as are involved in such handling and distribution of the materials.

I am or the opinion that the phenomenon of gelling of such solutions and compositions and their increase in bodyor viscosity as a whole are probably related to the phenomenon of separation, since when separation takes place in many cases'the separated phase containing larger proportions of zein is itself a gel in character; and since also in many cases compositions containing zein which tendto separate when the proportion of solvent to zein is as high as about 3 1 and higher will gel as a whole with lower proportions of solvent or higher concentrations of zein; and also since many solutions which are stable and do not separate when the proportion of solvent to zein is from 2 to 2.5 1 or higher will form gels as a whole if they contain higher proportions of zein. However, in the consideration of the tendency to gel and to increase in viscosity or body as referred to in the present application I have reference to the tendency of solutions to gel as a wholeor to increase in viscosity through their entire mass, in cases in which the proportions of solvent to zein are in the order of 2 to 2.5 1 and higher, up to 9 or 10 1, which are the solutions solutions. It is to be appreciated that solutions or compositions which are stable and in which the tendencies to gel and to increase in viscosity are adequately retarded or prevented within this range of concentrations may, with higher concentrations of zein, be more likely to form gels; but in any case the compositions prepared in accordance with the present invention will have a less tendency to form gels or to increase in viscosity than the solutions hitherto known.

In accordance with my present invention. I have found that substantially nongelling stable solutions of zein in relatively high-boiling substantially non-aqueous solvents can be formed directly without the addition of any water. The relatively high-boiling substantially non-aqueous solvents embodying my invention may suitably be one of the class of glycols such as, for example, diethylene glycol, triethylene glycol, propylene glycol, and the like, and preferably, those of higher molecular weight than ethylene glycol, or any mixture of these glycol solvents; or one of the class of closed chain alcohols such as the aryl and cyclic alcohols, for example, benzyl alcohol, furfuryl alcohol, cyclohexanol; or an alcohol derivative such as a ketone alcohol, for example, diacetone alcohol, free from acetone; or any mix- .ture of these relatively high-boiling solvents. Whle zein is soluble, as hereinafter set forth, in these relatively high-boiling solvents without added water, the use of small amounts of water up to about 5% in these solvents is not precluded.

The solutions or coating compositions of zein in these relatively high-boiling solvents produced in accordance with the present invention, are stable on standing at temperatures of F. and below and do not separate even when cooled to temperatures of 50 to 70 F. and somewhat below. When cooled to temperatures as low as 10 above zero or to zero, solutions prepared in accordance with the present invention may separate and become solid; however, on heating again to temperatures of from about 45 to 70 F., a re-solution is effected either without, or with slight stirring, and the solutions return to the normal form at the re-heating temperatures. The stable solutions prepared in accordance with the present invention have very little tendency to thicken and gel and in some instances practically no tendency to thicken or gel over practical periods of time in the order of 3 to 6 months. They contain no added water, or only small amounts of added water up to about 5%, and are, therefore, substantially non-aqueous.

In producing solutions or coating compositions in accordance with my invention, the zein or other prolamin is mixed with any one or more of the relatively high-boiling direct alcohol or alcohol derivative solvents, for example, diethylene glycol, diacetone alcohol or benzyl alcohol. The mixing may be effected in any suitable vessel or container such as, for example, a kettle, usually with some stirring and with the application of heat generally higher than F. and suitably in the order of about to 250 F. and higher, depending on the particular solvent or mixture of solvents utilized. A stable, substantially nongelling solution or coating composition in these direct relatively high-boiling alcohol solvents is obtained generally in about 5 to 25 minutes and in most instances satisfactory solutions or coatings are obtained in about 5 to 15 minutes with the utilization of temperatures in the order of about 110 to 225 F., the time and temperatures being"I influenced by the quantities'of materials The quantity of direct relatively high-boiling alcohol solvent necessary to effect a substantially nongelling stable solution or coating composition of the zein is suitably in the order of about at least 3 parts by weight of the solvent to about 1 partby weight of zein. In some instances as, for

example, with benzyl alcohol, 2 parts by weight of the solvent to 1 part by weight of the zein is sufflcient to produce asubstantially nongelling stable solution or coating composition in accordance with my invention. In general, satisfactory solutions or coating compositions may be obtained with the use of from about 3 to 20 or more and preferably 3 to 9 parts by weight of the solvent to 1 part by weight of zein. The most practical working solutions or coating compositions are obtained with the use of 3 to 5 parts by weight of the solvent to 1 part by weight of the zein.

It is, of course, obvious that the viscosity of coating compositions obtained in accordance with my I invention is at least in part dependent onvthe proportion of solvent used. Y

The following examplesare illustrative of the methods for producing coating compositions embodying my invention which are substantially nongelling over practical periods of time; in many cases over from 3 to -6 months. In these examples, the term "parts indicates parts by weight.

Example 1 10 parts of zein are mixed with 30 parts of benzyl alcohol in a suitable vessel. On stirring and with ,the application of a slight heat in the order of about to F., a clear, brilliant, stable solution of the zein in the benzyl alcohol is obtained in about 5 to 15 minutes. The solution is rather viscous.

Example 2 10 parts of zein are mixed with 50 parts of benzyl alcohol in a suitable vessel. On stirring the mixture and with the application of slight.

heat in the order of about 110 to 115 F., a clear, brilliant, stable solution of the zein is obtained in about 5 to 10 minutes. The solution obtained is less viscous than that obtained by the method of Example 1.

Example 3 10 parts of zein are mixed with 40 parts of cyclohexanol in a suitable vessel. On stirring and with the application of heat in the order of about to F., a stable solution of the zein in the cyclohexanol is obtained in about 7 to 12 minutes.

Example 4 10 parts of zein are mixed with 30 parts of diethylene glycol in a suitable vessel. On stirring the mixture at room temperature the zein is converted into a viscous, translucent, semiplastic mass. On the application of heat in the order of about 150 F. and with continued stirring, a clear, stable solution of the zein in the diethylene glycol is obtained in about 5-to 10 minutes.

. Example 6 10 parts of zein are mixed with 40 parts of triethylene glycol. On stirring and with the application of heat in the order of to a clear, stable solution of the zein in the solvent is obtained in about 6 to 12 minutes.

Example 7 10 parts of zein are mixed with 40 parts of propylene glycol. On stirring and with the application of heat in the order of 130-1 40 F., a clear, bright, stable solution of the zein in the solvent is obtained in about 5 to 10 minutes.

Example 8 Example 9 10 parts of zein are mixed with 50 parts of diacetone alcohol in a suitable vessel. On stirring and with the application of heat in the order of 210 F. a slightly cloudy solution is formed in about 12. to 20 minutes. On cooling and standing, this solution becomes quite viscous and turns rather clear.

The coating compositions embodying my invention have the unusual property, particularly Whenrheated, of being able to give up their solvent or solvents readily when applied to any surface and they readily form tough, flexible, non-tacky, hard and generally transparent films. The films are very strong and have unusual adherent properties. With the aid of these coating compositions the film forming. properties thereof can be built up to produce a film of greater toughness, flexibility, hardness and gloss than is capable of being formed from coating compositions containing added water in an amount greater than 5%. Under normal temperature conditions the solutions produced in accordance with my invention will produce nonblushing coatings, on drying, without the aid of supplementary anti-blushing agents as in the prior art. These coating compositions may be applied to any surface and they may be used for coating, sizing, impregnating and waterproofing any material such as paper, textiles, wood, wood pulp and the like. -When coated on paper, Cellophane, glass and the like, a film is formed almost immediately which possesses the film characteristics set forth above. Since these coating compositions have decided adhesive properties, they may be used either per se or in combination with other materials for uniting or laminating paper, cloth, wood, glass, felt, Cellophane, metals and metal foils and the like.

The characteristics of the coating compositions embodying my invention, and hence of the ultimate films formed therefrom, can be altered at will and as desired by the inclusion of diluents, modifiers, plasticizers and fillers, as set forth in my prior copending application, Serial No. 158,- 215, filed August 9, 1937. The characteristics such as spread and flow of these coating compositions may also be modified by the addition of a fatty acid such as, for example, oleic, linseed, hemp seed, lauric and like fatty acids, by the inclusion of blown or bodied drying oils, such as blown China-wood oil or other oxidized oils, and by the inclusion of cetyl, lauryl, myristyl and like fatty alcohols having 8 or more carbon atoms in the chain. If desired, compatible natural and synthetic resins such as, for example, rosin, sandarac, copal, phenol-aldehyde, ureaaldehyde, glycerine-phthalic anhydrid, vinyl and like resins, or compatible cellulose derivatives such as, for example, high and low viscosity nitrocellulose, cellulose acetate, ethyl cellulose and like cellulose derivatives may be incorporated in the coating compositions in varying proportions to meet any desired needs.

In the claims, when I use the expression substantially non-aqueous", I refer to solutions or coating compositions containing no added water or only small amounts of added water up to about 5%; and when I use the expression stable" I refer to solutions or coating compositions which, when the concentration of zein in the solvent varies from about 1 part by weight of the zein to about at least 3 parts by weight of the solvent, the solutions do not separate on standing or even when cooled to a temperature of 50 to 70 F. and somewhat below. When I use the expression nonge1ling" I refer to solutions or coatings which in general have very little tendency to thicken and gel and in some instances practically no tendency to thicken and gel over practical periods of time.

I claim:

1. A substantially non-aqueous coating composition comprising a substantially non-aqueous solution of zein comprising about 1 part by weight 2. A substantially non-aqueous coating composition comprising a substantially non-aqueous solution of zein comprising about 1 part by weight of zein and at least about 3 parts by weight of propylene glycol containing not in excess of 5% of water which is stable as regards separation at temperatures of 70 F. and which is substantially nongelling, said composition containing not in excess of about 5% of added water.

3. A substantially non-aqueous coating composition comprising a substantially non-aqueous solution of zein comprising about 1 part by weight of zein and at least about 3 parts by weight of triethylene glycol containing not in excess of 5% of water which is stable as regards separation at temperatures of 70 F. and which is substantially nongelling, said composition containing not in excess of about 5% of added water.

4. A substantially non-aqueous coating compo--.

sition comprising a substantially non-aqueous solution of zein in a direct glycol solvent wherein at least about 3 parts by weight of the solvent are combined with l part by weight of zein and which is stable as regards separation at temperatures of 70 F. and which is substantially nongelling, said solvent containing not in excess of 5% of water and said composition containing not in excess of about 5% of added water.

5. A substantially non-aqueous coating composition comprising a substantially non-aqueous solution of zein comprising about 1 part by weight of zein and at least about 3 parts by weight of a glycol solvent having a molecular weight higher than ethylene glycol which is stable as regards separation at temperatures of 70 F. and which is substantially nongelling, said solvent containing not in excess of 5% of water and said compo- 4- arcane f sition containing not in excess of about of added water.

6. A substantially non-aqueous solution of zein comprising about 1 part by weight of zein and at g separation at temperatures of 70 F. and which is substantially nongelling, said solvent containing 1 not in excess of 5% of water and said solution containing not in excess of about 5% of added water.

'7. .A substantially non-aqueous coating composition comprising a substantially non-aqueous sou lution of zein comprising about 1 part by weight of zein and at least aboutsS parts by weight of a solvent comprising a glycol having a molecular weight higher than ethylene glycol which is stable as regards separation at temperatures of 70 F.

I n and which is substantially nongelling, said solvent containing not in excess of 5% of water and v said composition containing not inexcess of about 5% of added water.

8. A substantially non-aqueous coating com-- 35 position comprising a substantially non-aqueous solution of zein comprising about 1 part by weight of zein and at least about 3 parts by weight of a mixture of ethylene glycol and a glycol having a higher molecular weight than ethylene glycol a which is stable as regards separation at temperatures of 70 F. and which is substantially nongelling, said mixture of glycols containing not in excess of 5% of water and said composition containing not in excess 01' about 5% of added water.

9. A- substantially non-aqueous coating composition comprising a substantially non-aqueous solution oi. zein comprising about 1 part by weight or zein and at least about 3- parts by weight of a mixture of ethylene glycol and diethylene glycol 5 which is stable as regards separation at temperatures of 70 F. and which is substantially nongelling, said mixture of glycols containing not in excess of 5% or water and said composition containing not inexcess oi about 5% added water.

10. A substantially non-aqueous coating composition comprising a substantially non-aqueous solution of zein comprising 1 part by weight of zein and from about 2 to about 10 parts by weight of a solvent comprising a glycol having a molec- 16 ular weight'higher than ethylene glycol which'is stable as regards-separation at temperatures of 70 F. andwhich is substantially nongelling, said solvent containing not in excess "01 5% of water and said composition containing not in excess of 20 about 5% of added water.

11. A substantially non-aqueous coating composition comprising a substantially non-aqueous solution of a .prolamin comprising 1 part by weight of the prolamin and from about 2 to about 10 parts by weight or a solvent comprising a glycol having a molecular weight higher than ethylene glycol which is stable as regards separation at temperatures of F. and which is substantially nongelling, said solvent containing not in excess of 5% of water and said composition containing not in excess of about 5% of added water.

ROY E. COLEMAN. 

